Production of hydrocarbons



Feb. 4, 1941. J. s cAREY PRODUCTION OF HYDROCARBONS rma hun, 1937 Patented, Feb. 4, 1an

UNITI-jo 4sl'lfrri:

s PATENT OFFICE f rnonuo'rron or nr'naoomons ames S. Carey, Cranford, N.,J., assignor to The M. W. Kelloggr Company, New York, N. Y., a

corporation of Delaware Appuccucn February 11, 1931, scri-.1 No. 125,119

e 5 claim. (c1. lss-1o).

l This invention relates to the production of,

ethylene, andv more particularly to the production of ethylene and a normally liquid fraction from va mixture of gases comprising xed gases,.such 5 as hydrogen and methane, and Cz, C: and C4 hydrocarbonaincluding both oleiins and parafilns, such as a gas resulting from an oil cracking operation.

It is an object of Ithe invention to provide a continuous -process of producing ethylene wherein a gaseous stream, such as described above, is

converted to ethylene, fixed gases, fuel oil and a fraction within the motor fuel boiling range. It is a further object to provide a process of producing ethylene from a. mixture of gases of the nature describedwherein the refrigerant necessary' 2,5 tion, and the invention is not necessarily limited l by the physical limitations of the apparatus illustrated but is capable of other modifications.

Referring to the drawing for a detailed description of an .example of the invention, a streamA of gases-comprising fixed gases, such as hydrogen and methane and C2,l C3 and Cc hydrocarbons, including both oleflns and parafns, such as the overhead from a stabilizer in an oil cracking apparatus, is introduced to the'system in line 35 I and is passed to fractionating tower 2 wherein the pressure is maintained at the degree necessary to carry on a fractionation of the gaseous 'stream into an overhead which contains substantially all the ethylene contained in the gaseous 40 stream, together with lighter gases, and a condensate containing substantially all the ethane contained in the gaseous stream, together. with 'heavier gases. vThis separation may be accomplished, for example, by maintaining the'fractionating tower- 2 at a pressure of yabout 495 pounds per square inch absolute with a temperature of about 20 F. at the top of the tower. The pressure is effected by means of compressor l in line l. and the incoming gases are ordinarily Aso cooled by passage throughcooler 4. The overhead gases from tower 2 are withdrawn through line 5 and passed through cooler l wherein they Aare refrigerated to condense a portion thereof. This may be accomplished by cooling them to a -degree whereby they emerge from cooler B at a 'some ethylene.

, temperature of approximately 60 F. The mixtureof condensate and uncondensed gases is separated in separator 1, and the condensate is returned 'as reux to tower 2 through line l lby means lof pump 9. The overhead gases in line 6 may contain a small proportion of ethane and heavier gasesso that the partial condensation and separation in separator 1 eiiect a further removal of ethane from the'gaseous stream, a large proportion ofwhich is condensed together with m The return of these condensed gases to fractlonating tower 2 is regulated to .maintain the proper temperature at the top of tower 2.

The uncondensed gases are withdrawn from 15 separator 1 through line il and consist of any hydrogen, methane, and substantially all the ethylene contained in the gases introduced' in fractionator 2 with, at most, a minor proportion of gases of higher molecular weight. The gases .20'

pass through line vlo to fractionating tower Il, which is preferably maintained at the same pressure as tower 2 and wherein ethylene is separated from fixed gases by suitable regulation of tem' perature. lorexample,` with 'a pressure of 495 25 pounds per square inch absolute in tower Il the top temperature may suitably be maintained at fr about -30 F. The gases which lpass overhead from tower Ii through line i2 contain substantially all the fixed gases. introduced to tower 2 30 with at most a minor proportion of'ethylene, a major proportion of the ethylene having been condensed and reiiuxed to the bottom of tower ii.. The overhead gases from tower il withdrawn through line i2 are refrigerated in cooler 35 I3 to condense a portion thereof including substantially all the ethylene and some methane,

which condensate is separated in separator Il and returned to tower il through line l5v by means of pump i6 -whereby the proper tempera- 40 ture is maintained in the top of tower Ii. The

refrigeration of the gases in cooler Il may be suitably carried out whereby they emerge from thecooler at a temperature of about- F. The xed gases are withdrawn from separator i4 45 through line Ii and may be suitably utilized elae where as a source of energy and refrigeration. by n expansion and heat exchange.

.To eilecta complete removal of nxed gases from the ethylene cooled in the bottom of tower il 5o a temperature of about 40 F. may be maintained under the conditions set forth above by means of, for example, the reboiling of a portion thereofA and its return to the tower Il, by means of circuit ls, which includes heatv exchanger Il. as

Ethylene, which is a product of the system, is withdrawn from the bottom of tower through line 64.

'I'he condensate collected in the bottom of tower 2 may be maintained at a temperature, under the conditions set forth above, of approximately 100 F. to facilitate the removal of fixed gases and ethylene therefrom. This maybe effected by reboiling a portion thereof and returning it to the tower 2, by means of circuit 20 which contains heat exchanger 2|.4

Condensate `is withdrawn from fractionating tower 2 through line 22 and maybe released to a substantially lower pressure by meansV of valve l5 23. 'The condensate is` introducedsto fractionating tower 24 from line 22, which fractionating tower is suitably maintained at conditions of temperature and pressure to effect a separation of ethane from heavier gases. For example,

` tower 24 may be maintained at apressure of approximately 265 per square inch absolute with a temperature in the top of the tower of about VF. 'I'he heavier hydrocarbons collect in the bottom of towler 24 and are maintained 25 at a .temperature suflcient to facilitate the complete removal of ethane therefrom, for example,

under the 'conditions set fonth above at a temperature of about 170; F. Themaintenance of this temperature may be accomplished by with- 80 drawing a portion of the liquid from the bottom of tower 24, reboiling it and returning it to .tower 24,'by means of circuit 26 which contains heat exchanger 26. o

The overhead gases from tower 2-4, consisting 85 essentially of substantial-ly all the ethane intro- -f duced -to tower 2 and containing at most 'a minor proportion of heavier hydrocarbons, are withdrawn through line 21 andl are passed through cooler 28 wherein they are refrigerated'to a den c gree sufcient to condense a portion thereof, said condensate consisting of substantially all hydrocarbons heavier .than ethane contained in the overhead. and including a portion of the ethane. To effect such condensation the gases may be cooled inv cooler 28 Ito a degree whereby they emerge from cooler 23 at a temperature of about .f 10 F.l The mixture of gases and condensate isv introduced to separator 29 wherein theconden- 5G sate collects in the bot-tom of the separator, and

the uncondensed gases pass overhead through line 30, valve 3| beingl provided to maintain the pressure in the separator 29. A portion of the condensate in` separator 29 is returned to tower 24- 36 through cooler 6 whereby the expanded condensate acts as the refrigerant in refrigerating the overhead gases from tower 2 to a suitable temperature, for example, to a temperature of 60 F. The gases resulting from the expansion of the condensate through cooler 6 are returned. to line 2l by means of compressor 31 and arereturned for-condensationin cooler 28.,

A third portion of the condensate inseparator 29 may be withdrawn therefrom through lines 34 and' 38 and expanded by Ymeans of valve 39 .through pooier I3 wherein the expanded condensate acts as the refrigerantin cooling the overhead gases in line |2, for example, .to a temper- 'ature of -,70 F. The gases resulting from they expansion of the condensate are returned to line j 21 `by means -of compressorA 4|)1 and are returned forcondensation in cooler 28. v

The refrigerant for cooler 28 may be ammonia supplied from a'suitable source and cooled, for

example, to -a temperature of -7 F., or the refrigerant may -be suitably cooled andvcompressed propane, produced from .the system, as describedV below.

Any condensatein separator 29 notutilized .as reflux orv refrigerant vmay -be 4'withdrawn through lines 34 and 4| and combined -with'lthe overhead gases from-.separator 29 in line 30.

The condensate from the'bottom of tower 24 withdrawn through line 44,' consisting-essentially of liquefied C3 and C4 hydrocarbons,A and the gases in line 30, consisting essentially of ethane, are passed to cracking coils 42 and '43, respectively, whereinA they are heated to the temperatures appropriate to effect the most eflicien't cracking of each, with a view to producing a maximum of ethylene. For example, the C3 andl C4 hydrocarbons may bel heated .to a temperature of approxiln'iately 1450 F., andthe ethane may be heated to a temperature of approximately 1600 F., the pressure being 0 to 400 pounds per square inch in each coil. The ethane and the C3 and C4 hydrocarbons may be suitably utilized as -the refrigerants in various coolers in the system, for example, coolers 4, 53 and 59 may be suitably preheated (by meansnot shown) preliminary to cracking. I

The cracked products from both cracking oper- `ations, withdrawn through line 4.5, are suitably quenched, as described below, and passed to fractionating tower 46, which may be maintained suitably ata pressure of 40I pounds per square inch absolute. Infractionator 46 the temperatures are maintained to produce an overhead including the normally gaseous hydrocarbons and j a portion of -thehydrocarbons in thefmotor fuel boiling range. For this purpose a top temperature of about-.250" F. may be suitably maintained by refluxing. A side stream i's Withdrawn from tower 46'by pump 41 and circulated through reboiler circuit 48 which passes successively through-heat exchangers 26, 2| and`vl9. A portion 'of the side stream passing through the reboiler circuit may be withdrawn through line 49 and used as vthe quench for the cracked products in line `45, valves 50 being provided to regulate lthe quantity of quench used.

The heavy hydrocarbons produced in the cracking operations are collected in the bottom .of tower 46 where a temperature of about 725 F. is suitably maintained, and bottoms, suitable for fuel oil are removed through line-5| The overhead from tower 46 is withdrawn through line 52, passed through .cooler 53 wherein it is cooled `to condense a portion thereof,

which is collected in separator 54 and returned .as reflux to tower 46 through line 55 by means of pump 56 to maintain the proper .temperature in the ,top of tower 46. The ,uncondensed gases separated in separator 54, consisting ofxed gases and C2, Ca and C4 hydrocarbons, together with heavier hydrocarbons in the motor fuel -boili-ng range. are withdrawn through line 5l, compressed and cooled bycompressor 58.and cooler 59 to condense the -hydrocarbons having more than 4 carbon atomsin each molecule and passed to separator 60 wherein the uncondensed gases and the condensate areseparated. The condensate, consisting of hydrocarbonsin the vmotor fuel boiling range, is withdrawn from sep- -arator 50 through line 6| and may 4be passed to the assumer' t: an on crscnng system 4'rae uncondensed gases, which may havesubstantially the composition of the gas stream introduced in ratus necessary for its A operation may be omitted.

Alternatively, the C; .and C; -hydrocarbons withdrawn from the bottom of tower 24 throughv line Il may be fractionated to separate them into v a fraction consisting essentially of C; hydrocarbons and a fraction consisting essentially of C4 hydrocarbons. The C; fraction may be then used as the refrigerant in the, cooler 28 by expanding it through line t! in a manner similar to the expansion of the condensate from. sepa- 'rator 29 through line 35 and cooler t. With such operation the C; and C4 hydrocarbons may be separately subjected to cracking operations best suited to produce efllcient cracking withV a maximum production of ethylene, or they may be combined and subjected to a single cracking operation, as shown above.

Fractionating towers 2, Il, 24, and It are provided with suitable trays to provide intimate contact of the gases and liquids contained therein for carrying on the condensation, stripping,

and vaporizing operations necessary to effect the'l desired fractionation. It is apparent also that means for maintaining the proper temperatures in the bottoms'oi these towers, other than that shown, may be provided within the scope of the invention. v

The invention provides a continuous process for the production of ethylene reither in a substantially Dure state or in admixture with fixed.l

gases. The fractionation of the gases in tower 2 'necessitates the use of a refrigerant to maintain the proper temperature in the topof tower 2, having an extremely low boiling point. It is an advantage of the present invention that the process provides such a refrigerant in the formof the condensate in separator 29 as an intermediate product. lThis condensate serves to remove substantially the last portion ofr hydrocarbons heavier than' ethane Ifrom the overhead gases from tower and serves as the reflux for maintaining proper .temperature conditions in tower 2l and as the refrigerant for cooler i merely by the expansion of the condensate against the proper vacuum provided by compressor 31. Where it is desired to separate ethylene from the fixed gases this separation is facilitated by the use, of condensate from separator 29 as refrigerant in the same manner of utilization as in cooler t whereby a portion of the condensate is'expandedthrough cooler I3 against a vacuum maintained by compressor 4l.

The invention therefore provides an eil'icient, self-contained process which provides its own "refrigerant, requiring merely the passage of a conventional refrigerant such as ammonia through line ofthe cooler 2l. v

'I'he separation of ethane fr om the heavier hydrocarbons also facilitates the eiiicient cracking of the ethane to produce a cracked product containing a maximum proportion of ethylene and of the cracking ofthe C: and C4 hydrocarbons to produce a cracked product containing-a maximum proportion ofl ethylene. The fixed gases maybe utilized as hereofore, and the fraction in the boiling range of -motor fuel may be suitably passed to astablliz'er in an oil cracking system, which stabilizer may -be the source of the feedgases.

It is to be understood that the foregoing description refers primarily to an illustrative embodiment of the invention, which invention is without departing from its essential scope.

I claim: i., l. 'I'he method o'f treating a stream of gases comprising essentially normally gaseous paraf-4 flnic and oleilnic hydrocarbons having from one to four atoms in each molecule to produce ethylene therefrom. which comprises, fractionating capable of other 'embodiments 4and variations'- said s tream into aiiquid substream containing a major proportion of"I the ethane and-higher boiltion of the ethylene and lighter components of said stream, fractionating the ethane substream to produce a gaseous overhead containing substantially all the ethane of said substream, refrig' erating said ethane overhead under pressure to liquefy a portion thereof, expanding a portion of said liquefied ethane overhead in indirect contact with the ethylene overhead from the firstmentioned fractionationv to liqueiy a portion thereof, and reiluxing said" liquenedethylene overhead to said first-mentioned fractionating operation. I

2. The method of treating a stream of gases comprising essentially. normally gaseous parafnic and oleilnic hydrocarbons having from` one ing hydrocarbons of said stream and a gaseous .4 overhead substreamcontaining a major proporto four atomsA in each molecule to produce ethyl' eneV therefrom which comprises, fractionating said stream into a liquid substream containing a major proportion of the ethane and higher boiling hydrocarbons of said'stream and a gaseous overhead subst'ream containing a major proportion of the ethylene and lighter components of said stream, fractionating the ethane substream to produce a gaseous overhead containing suby stantially allthe ethane ofsaid substream, refrigerating said ethane overhead under pressure to liquefy a portion thereof, expanding a portion of said liqueiled ethane overhead in indirect contact with the ethylene overhead from the firstmentioned fractionating operation to liquefy a portion thereof,'reiiuxing said liquefied ethylene overhead tov said fractionatingoperatiom fractionating the ethylene substreamto produce a gaseousV overhead comprising essentially fixedv gases and a liquid fraction consisting essentially of liquefied ethylene and containing substantially all the ethylene contained in said substream, and expanding another portion of said -liqueiied ethane overhead in indirect contact with the gaseous overhead from the fractionation of said' ethylene substream to liquefy a portion thereof and reiluxing said liquefied gaseous overhead to said fractionating operation.

3.`The method of treating a stream oflgases comprising essentially normally gaseous' parafiinic and ole'iinic hydrocarbons having from one to four'atoms in each molecule to produce ethylene therefrom which comprises, fractionating said stream into a vliquid substrearn costainin' Aa majorV proportion' of the ethane and higher boiling'hydrocarbons of said stream and a gaseous overhead substream containing a m or proportion of the ethylene and lighter o'o ents of said stream; fractionating the ethane substream to produce a gaseous overhead containing substantially all the ethane of said substream. refrigeratingsaid ethane overhead under pressure to liquefy a portion thereof, expanding a portion of said liqueed; ethane overhead in indirect lcontact with the ethylene overhead from the first-mentioned fractionation to liquefy a portion thereof, a refluxing said liquefled ethylene overhead to said first-mentioned fractionating operation, separately cracking the unliquefled portion of the ethane overhead. and the Ca and C4 hydrocarbons constituting the condensate from the fractionation of the ethane subfraction to convert at least a portion thereof to ethylene, separating from the cracked products substantially al1 hydrocarbons containing more than four carbon atoms. in each molecule, and adding the remaining lighter cracked products to said stream vprior to said first-mentioned fractionation, Y

4. The method of treating a stream of gases comprising essentially normally gaseous parafnic and oleflnic hydrocarbons havingfrom one said stream into a liquid substream containing'` a major proportion of the ethane and higher s to four atoms in each molecule toproduce ethylene therefrom which comprises, fractionating boiling hydrocarbons of said stream and a gaseous overhead substream containing a major proportion of the ethylene and lighter components ot .said stream, fractionating the ethane substream to produce a gaseous overhead containing substantially all the ethane of said sub-` stream, refrigerating said ethane overhead under pressure to liquefy` a portion thereof and refluxing a portion oi' said liquefied ethane overhead to the fractionation of the ethane substream, vexpandingl a portion of said liquefied ethane overhead in indirect contact with ,the ethylene overhead from the nist-mentioned fractionation to liquefy a portion thereof, and reluxing saidl liquefied ethylene overhead to said first-mentioned fractlonating operation.

5. The method of treating a stream of gases comprising essentially normally gaseous parafnic and oleflnic hydrocarbons having from one tolfour atoms in each molecule to produce ethylene therefrom which comprises, fractionating said stream into' a liquid substream containing a major proportion ofthe ethaneand higher f boiling hydrocarbons of said .stream and a gaseous overhead substream containing -a major proportion of the ethylene and lighter components o f said stream, fractionating the ethane substream to produce a gaseous overhead containing substantially all the ethane of said substream,

refrigerating said ethane overhead under pressure to liquefy a portion thereof, fractlonating the ethylene substream to produce a gaseous overhead comprising essentially fixed gases and a liquid fraction consisting essentially of liqueed ethylene and containing substantially all the ethylene contained in said substream, and expending a portion of said liquefied ethane overhead in indirect contact with the gaseous overhead from the fractionation of said ethylene substream to liquefy a portion thereof and refluxing said liquefied gaseous overhead to said fractionating operation.

f JAMES S. CAREY. 

